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| United States Patent |
5,502,137
|
|
Matayabas, Jr.
, et al.
|
March 26, 1996
|
Polyether glycols and alcohols derived from 3,4-epoxy-1-butene,
tetrahydrofuran and an initiator
Abstract
Disclosed are novel polyether compounds obtained by the reaction or
polymerization of 3,4-epoxy-1-butene in the presence of tetrahydrofuran,
an acidic catalyst and a nucleophilic initiator compound. The polyether
compounds comprise m units of residue (1), n units of residue (2), and p
units of residue (3) wherein (i) residues (1), (2) and (3) have the
structures:
##STR1##
(ii) the total value of m+n+p is 5 to 70; (iii) the value of n/(m+n+p) is
in the range of 0.2 to 0.4, i.e., residue (2) constitutes from 20 to 40
mole percent of the total moles of residues (1), (2) and (3); and (iv) at
least 98 percent of the terminal groups have the structure:
##STR2##
| Inventors:
|
Matayabas, Jr.; James C. (Kingsport, TN);
MacKenzie; Peter B. (Kingsport, TN);
Hyatt; John A. (Kingsport, TN)
|
| Assignee:
|
Eastman Chemical Company (Kingsport, TN)
|
| Appl. No.:
|
344905 |
| Filed:
|
November 25, 1994 |
| Current U.S. Class: |
528/393; 528/417 |
| Intern'l Class: |
C08G 065/14; C08G 065/08 |
| Field of Search: |
528/421,393,417
526/273,332
|
References Cited
U.S. Patent Documents
| 3133905 | May., 1964 | Snyder et al. | 528/393.
|
| 4500705 | Feb., 1985 | Copelin | 528/417.
|
Other References
Bartlett, J. Am. Chem. Soc., 70, 926 (1948).
Ivanchev, J. Polym. Sci., Polym. Chem. Ed., 18, 2051-2059 (1980).
Kubisa, Makromol. Chem., Macromol Symp., 13/14, 203 (1988).
Brzezinska, Makromol. Chem., Rapid Commun., 7, 1 (1986).
Bednarek, Makromol. Chem., Suppl., 15, 49 (1989).
Biedron, Makromol. Chem., Macromol Symp., 32, 155 (1990).
|
Primary Examiner: Schofer; Joseph L.
Assistant Examiner: Cheng; Wu C.
Attorney, Agent or Firm: Thomsen; J. Frederick, Gwinnell; Harry J.
Claims
We claim:
1. A polyether polymer comprising m units of residue (1), n units of
residue (2), and p units of residue (3) wherein (i) residues (1), (2) and
(3) have the structures:
##STR9##
(ii) the total value of m+n+p is 5 to 70, (iii) the value of n/(m+n+p) is
in the range of 0.2 to 0.4, and (iv) at least 98 percent of the terminal
groups have the structure:
##STR10##
2. A polymer according to claim 1 wherein the value of n/(m+n) is in the
range of 0.25 to 0.45 and the polymer has a polydispersity value of less
than 4.
3. A polyether polymer comprising m units of residue (1), n units of
residue (2), and p units of residue (3) wherein (i) residues (1), (2) and
(3) have the structures:
##STR11##
(ii) the total value of m+n+p is 10 to 40, (iii) the value of n/(m+n+p) is
in the range of 0.3 to 0.4, (iv) the value of n/(m+n) is in the range of
0.35 to 0.45, p/(m+n+p) is less than 0.15, and (v) at least 98 percent of
the terminal groups have the structure:
##STR12##
4. A polymer according to claim 3 wherein the polymer has a polydispersity
value of 1 to 2 and is comprised of at least 80 weight percent of residues
derived from 3,4-epoxy-1-butene and tetrahydrofuran.
5. A polymer according to claim 3 wherein the polymer has a polydispersity
value of 1 to 2 and is comprised of about 5 to 20 weight percent, based on
the weight of the polyether polymer, of hydroxyl initiator residues.
Description
This invention pertains to certain novel polyether compounds. More
specifically, this invention pertains to polyether glycols and alcohols
containing repeating units of the structure:
##STR3##
This invention also pertains to a process for the preparation of the
polyether compounds by the polymerization of 3,4-epoxy-1-butene in the
presence of certain strong acidic catalysts, tetrahydrofuran, and a
hydroxyl initiator compound.
U.S. Pat. No. 3,133,905 discloses the copolymerization of small amounts of
3,4-epoxy-1-butene with tetrahydrofuran using as catalyst boron
trifluoride to give a copolymer comprising about 90 mole percent residues
of tetrahydrofuran and only 10 mole percent residues of
3,4-epoxy-1-butene. However, only about two-thirds of the available
3,4-epoxy-1-butene is incorporated into the copolyether, and the
repeat-unit structure is not disclosed. S. S. Ivanchev, et al., J. Polym.
Sci., Polym. Chem. Ed., 18, 2051-2059 (1980), investigated the
homopolymerization of 3,4-epoxy-1-butene with boron trifluoride etherate
and disclose that the rate of termination is much faster than the rate of
propagation, leaving much of the 3,4-epoxy-1-butene unreacted. Our
investigation of this chemistry corroborates this result, i.e., low yields
of a thermally-unstable, white material are obtained and the
chloroform-soluble portion of the material contains only residue (1).
The disclosure of U.S. Pat. No. 3,133,905 differs from the present
invention in a number of ways. For example, the polyethers of the present
invention are prepared using a nucleophilic compound as an initiator for
the copolymerization of 3,4-epoxy-1-butene and therefore contain residues
derived from the nucleophilic initiator. Another difference is that the
novel unsaturated polyether compounds of this invention comprise repeat
units of residue (2) in addition to residues (1) and (3). The novel
unsaturated polyether compounds of this invention comprise minor amounts
of residue (3) derived from tetrahydrofuran compared to the amount of
residues (1) and (2) derived from 3,4-epoxy-1-butene. Boron trifluoride,
which was employed in the preparation of the polyethers of U.S. Pat. No.
3,133,905 does not give residues (2) and suffers from deactivation during
the polymerization of 3,4-epoxy-1-butene.
Other references which pertain to the general state of the
3,4-epoxy-1-butene art are discusses below. P. D. Bartlett et al., J. Am.
Chem. Soc., 70, 926 (1948), disclose the sulfuric acid-catalyzed
methanolysis of 3,4-epoxy-1-butene to give 1-hydroxy-2-methoxy-3-butene.
A. M. Ross, et al., J. Am. Chem. Soc., 104, 1658 (1982), disclose the
acid-catalyzed hydrolysis of 3,4-epoxy-1-butene to produce a mixture of
3,4-dihydroxy-1-butene and 1,4-dihydroxy-2-butene in a 96/4 ratio.
Polymers comprising residues (1) and (2) are not contemplated by the
above-cited prior art, and the reactions exemplified employ an excess of
the nucleophile.
U.S. Pat. No. 2,680,109 discloses the polymerization of unsaturated
1,2-epoxides, including 3,4-epoxy-1-butene, in the presence of stannic
chloride and a small amount of water. British Patent 869,112 and U.S. Pat.
Nos. 3,031,439 and 3,417,064 disclose the copolymerization of
3,4-epoxy-1-butene with ethylene oxide and propylene oxide, using as
catalyst strontium carbonate containing a small amount of water.
U.S. Pat. Nos. 3,158,705, 3,158,581, and 3,158,591 disclose the
polymerization of 3,4-epoxy-1-butene to give polyethers consisting only of
residue (1), using as catalyst trialkylaluminum compounds prereacted with
water. These patents also disclose the copolymerization of
3,4-epoxy-1-butene with ethylene oxide, propylene oxide, and
epichlorohydrin, using as catalyst trialkylaluminum compounds prereacted
with water. U.S. Pat. No. 3,509,118 discloses the preparation of
unsaturated polyether glycols containing only residue (1) prepared by
n-butyl lithium cleavage of the high molecular weight polyethers prepared
by the polymerization of 3,4-epoxy-1-butene in benzene using
triethylaluminum prereacted with water.
U.S. Pat. No. 3,133,905 also discloses the copolymerization of a small
amount of 3,4-epoxy-1-butene with ethylene oxide using ethylene glycol as
the initiator and solid sodium hydroxide as the catalyst in a pressurized
resin pot. U.S. Pat. No. 3,468,847 discloses the copolymerization of
3,4-epoxy-1-butene, hexafluoroacetone, ethylene oxide, and propylene
oxide, using cesium fluoride as catalyst.
Tsuruta, et al., Macromol. Chem., 111, 236-246 (1968), disclose that
diethylzinc prereacted with water polymerizes 3,4-epoxy-1-butene to give a
54% yield of high molecular weight polyether containing only residue (1).
Tsuruta, et al., also disclose the isolation of a 3% yield of polyether
from 3,4-epoxy-1-butene and uncomplexed diethylzinc as catalyst having
evidence of internal double bonds residue (2)! by infrared spectroscopy.
Our investigation of this chemistry resulted in no isolable polymer.
A series of publications P. Kubisa, Makromol. Chem., Macromol. Symp.,
13/14, 203 (1988); K. Brzezinska, R. Szymanski, P. Kubisa, and S. Penczek,
Makromol. Chem., Rapid Commun., 7, 1 (1986); M. Bednarek, P. Kubisa, and
S. Penczek, Makromol. Chem., Suppl., 15 49 (1989); P. Kubisa and S.
Penczek, Am. Chem. Soc., Div. Polym. Chem., Polym. Preprints, 31(1), 89-90
(1990); and T. Biedron, R. Szymanski, P. Kubisa, and S. Penzcek, Makromol.
Chem., Macromol. Symp., 32, 155 (1990)! teach that the polymer
microstructure from copolymerization of propylene oxide and
tetrahydrofuran using boron trifluoride etherate and a glycol initiator is
determined by interplay of steric and electronic factors, with steric
factors prevailing to give copolyethers with about 55 percent secondary
hydroxyl groups and 45 percent primary hydroxyl groups. Further, they
teach that the major contribution of the electronic effects of the side
group is its influence on the basicity of the secondary hydroxyl of the
growing chain. Butylene oxide gives a greater amount of secondary hydroxyl
than does propylene oxide due to greater steric effects of the ethyl group
compared to the methyl group.
None of the prior art discloses our novel polyether compounds described in
more detail hereinbelow or a process whereby the novel polyether compounds
may be obtained. The polyether compounds provided by the present invention
are comprised of m units of residue (1), n units of residue (2), and p
units of residue (3) wherein the total value of m+n+p is 5 to 70, the
value of n/(m+n+p) is in the range of 0.2 to 0.4, i.e., residue (2)
constitutes from 20 to 40 mole percent of the total moles of residues (1),
(2) and (3), the value of n/(m+n) is in the range of 0.25 to 0.45, and
residues (1), (2) and (3) have the structures:
##STR4##
The unsaturated polyethers of this invention are further characterized in
that at least 98 percent of the terminal groups have the structure:
##STR5##
Therefore, at least 98 percent of the terminal hydroxyl groups are
primary, rather than secondary, hydroxyl groups.
The polyether compounds may be used in the preparation or formulation of
surfactants and other compositions analogous to compositions derived from
known polyether polymers. The unsaturated polyethers may be hydrogenated
to the corresponding saturated polymers which may be employed in the
manufacture of polyester-ethers useful, for example, in molding
compositions. It is known that hydroxyl-terminated polyethers wherein all,
or substantially all, of the terminal hydroxyl groups are primary are more
reactive and thus produce superior products when compared to analogous
hydroxyl-terminated polyethers wherein a significant portion of the
terminal hydroxyl groups are secondary hydroxyl groups. For example,
Wolfe, Rubber Chemistry and Technology, 50(4), 688-703, September/October
1977, teaches that titanate-ester-catalyzed melt condensation
polymerizations of poly(propylene glycol) having a number-average
molecular weight of about 1000 with dimethyl terephthalate and
1,4-butanediol give copolyester-ethers having low inherent viscosities and
poor properties compared to copolyester/ethers prepared using
poly(tetramethylene glycol) and poly(ethylene glycol) having similar
molecular weights. The low inherent viscosities and poor properties are
due to the relatively high secondary hydroxyl group content of the
poly(propylene glycol). Wolfe also discloses that the use of
poly(propylene glycol) end-capped with 10-20 weight percent of ethylene
oxide does not overcome the problem, as only a marginal improvement in
inherent viscosity was realized. Due to the higher reactivity of the
formed primary hydroxyl, end-capping polyethers having secondary terminal
hydroxyl groups with ethylene oxide to increase primary hydroxyl content
typically is only partially successful. In order to achieve a majority of
primary hydroxyl end groups, e.g., greater than 65 percent, large amounts
of ethylene oxide are needed and usually give concomittant formation of
long ethylene blocks and causes the resulting polyether to have reduced
hydrophobicity and thus limits the usefulness of the polyethers in the
manufacture of condensation polymers. The high content of primary,
terminal hydroxyl groups possessed by the polyether polymers of the
present invention renders the polyethers more reactive, and thus more
useful, for condensation reactions in general.
Poly(tetramethylene ether) glycol is the industry standard for the
preparation of high performance condensation polymers such as Hytrel
polymer and polyurethane ethers such as Lycra spandex polymer. Efforts to
incorporate a substiuted oxirane such as propylene oxide and butylene
oxide for purposes of price and performance give increased concentrations
of secondary hydroxyl groups. The polyethers of this invention overcome
this difficulty without the incorporation of ethylene oxide or oxetane.
The polyethers of this invention are fundamentally different from
ethoxylated copolyethers of tetrahydrofuran and butylene oxide, which are
expected to have increased hydrophobicity and decreased thermal stability
compared to poly(tetramethylene ether) glycol.
The process utilized to prepare the above-described polyether compounds
comprises polymerizing 3,4-epoxy-1-butene in the presence of a catalytic
amount of a strong protonic acid, tetrahydrofuran, and a nucleophilic
initiator compound to obtain the polyether compounds of the invention. The
polymerization mechanism involves living polymerization, provided that the
acid catalyst is not neutralized or otherwise rendered inactive, to the
extent that step-wise addition of 3,4-epoxy-1-butene monomer gives
step-wise increase in polymer molecular weight and molecular weight
control is readily achieved by the stoichiometry of monomer to initiator.
A wide variety of molecular weights may be achieved, but the molecular
weights are generally controlled to provide polymers with molecular
weights of about 500 to 3000 for use as polymer intermediates.
The polymerization process is carried out in the presence of
tetrahydrofuran which functions as both a comonomer and the process
solvent. The amount of tetrahydrofuran which may be employed ranges from
about 5 to 95 weight percent of the reaction solution. Tetrahydrofuran
functions as both solvent and comonomer; however, only minor amounts of
tetrahydrofuran are incorporated into the polyether and, even at
relatively low loadings, tetrahydrofuran is present in the reaction medium
even after completion of the polymerization. Incorporation of
tetrahydrofuran gives rise to residues (3), and the value of p/(m+n+p)
usually is less than 0.25 and typically is about 0.1. Comparative Example
1 demonstrates that the use of methylene chloride (rather than
tetrahydrofuran) as the process solvent gives a low value of n/(m+n) which
typically is about 0.20. The inclusion of tetrahydrofuran in the
polymerization mixture produces 2 favorable results: (i) the value of
n/(m+n) is higher than expected and (ii) the value of n/(m+n) remains
approximately constant over a wide range of molecular weights. These
results offer significant potential advantages. For example, the decreased
content of residues (1) and the resulting increased content of residues
(2) and (3) give polyethers which, upon hydrogenation, have a much reduced
content of residues having the structure
##STR6##
with concomitant increase in the content of residues (3). Such saturated
polyether materials possess improved properties such as, for example,
improved thermal stability. Furthermore, the ability to prepare
substantially the same composition at a variety of molecular weights is
desirable to potential users, and the use of tetrahydrofuran is
particularly advantageous because the content of residues (1) is more
constant over the range of molecular weights of interest. In addition,
discoloration of the unsaturated polyether is more easily controlled when
the polymerization is conducted in the presence of tetrahydrofuran. The
presence of tetrahydrofuran during polymerization results in reduced
viscosity which provides better mixing and improved heat transfer. In
contrast to reaction carried out in the absence of tetrahyrofuran (see
Comparative Example 3), the presence of tetrahydrofuran gives a more
constant composition as indicated, for example, by the ratio of n/(m+n) as
is shown in Example 5.
Comparative Example 2 demonstrates that when poly(tetramethylene ether)
glycol is used as the initiator, the selectivity for formation of residue
2 is not improved and the value of n/(m+n) remains at about the same low
value of 0.21. Thus, the presence of tetrahydrofuran and not
poly(tetramethylene ether) is responsible for the above described
advantages in the polymerization of 3,4-epoxy-1-butene. The polyethers and
the process of this invention differ from the copolyethers derived from
tetrahydrofuran and oxirane disclosed by Kubisa, et al., in that (i) the
polyethers of the invention contain essentially only terminal, primary
hydroxyl groups, (ii) the present process results in the incorporation of
only minor amounts of tetrahydrofuran into the polyether even though a
very large excess of tetrahydrofuran is used, (iii) in the present process
tetrahydrofuran exhibits a solvent effect on the stereoselectivity of the
polymerization of 3,4-epoxy-1-butene which favors residue (2), and (iv)
tetrahydrofuran exhibits a solvent effect of decreasing the rate of
conversion of 3,4-epoxy-1-butene to polyether.
The initiator compound may be selected from various nucleophiles such as
the hydroxyl compounds disclosed in Published International PCT
Application WO 89/02883. The initiator compound preferably is selected
from various organic hydroxyl compounds such as alcohols, polyols, i.e.,
polyhydroxyl compounds containing 2 to 6 hydroxyl groups, and
hydroxyl-terminated polymers such as hydroxyl-terminated polyether and
polyester polymers. When an alcohol is used as the initiator, the
polymeric product obtained has a hydroxyl group on one end of the chain (a
terminal hydroxyl group) and thus is a polymeric alcohol. The other end of
the polymer chain is terminated with the residue of the alcohol initiator,
e.g., a residue having the formula --O--R.sup.1 wherein R.sup.1 is the
residue of an alcohol, preferably an alkyl group, containing up to about
20 carbon atoms. When a polyhydroxyl compound is used as the initiator,
the polymer grows from at least 2 of the hydroxyl groups of the initiator,
and the subsequently-obtained polymer is a polyhydroxyl polymer. The
residue of the polyhydroxy initiators may be represented by the formula
--O--R.sup.2 -- wherein R.sup.2 is the residue of a polyhydroxy initiator.
Suitable alcohols include low molecular weight organic alcohols and
polymeric alcohols which may be linear or branched-chain aliphatic,
alicyclic or aromatic. Although secondary or tertiary alcohols may be
used, primary alcohols are preferred. Some typically useful alcohol
initiators include methyl alcohol, ethyl alcohol, n-butyl alcohol,
iso-butyl alcohol, 2-ethylhexyl alcohol, n-decyl alcohol, stearyl alcohol,
cetyl alcohol, allyl alcohol, benzyl alcohol, phenol, nonyl-phenol,
cresol, and the like. Typically useful glycol initiators include ethylene
glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol,
1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol,
2,2-dimethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol,
2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-dihydroxy-2-butene,
3,4-dihydroxy-1-butene, benzenediols such as hydroquinone and resorcinol,
and the like. Typically useful polymeric alcohols and glycols include
polyethylene glycol, polyethylene glycol monomethyl ether, polypropylene
glycol, polypropylene glycol monobutyl ether, poly(tetramethylene ether)
glycol, and the like. Low molecular weight, hydroxyl-terminated polyesters
also may function as the .hydroxyl initiator compound. Typically useful
polyols include glycerol, starch, sucrose, glucose, pentaerythritol, and
the like. Water also may be used as the initiator. Water and diols having
2 to 6 carbon atoms constitute the preferred initiators, i.e., wherein
R.sup.2 is alkylene of 2 to 6 carbon atoms.
The catalyst employed in the preparation of the novel polyethers described
herein must be a strong protonic acid and may be either in liquid form or
may be incorporated or contained within a solid resin. The acidic catalyst
may be derived from a mixture of a Lewis acid and water, an alcohol or a
weak protonic acid. Suitable acid catalysts include tetrafluoroboric acid,
perchloric acid, strongly acidic ion exchange resins (e.g., Amberlyst
resins) and fluorosulfonic acids such as perfluoroalkanesulfonic acids
containing up to about 6 carbon atoms (e.g., trifluoromethanesulfonic
acid), fluorosulfonic acid, and perfluorosulfonic acid polymers (e.g.,
Nafion resins), and the like. An example of a fluorosulfonic acid polymer
is Nafion.RTM.NR-50 (.RTM.E. I. du Pont de Nemours & Co.), available from
Aldrich (catalogue No. 30,938-9). The most effective and, therefore, the
preferred catalysts are the perfluoroalkanesulfonic acids such as
trifluoromethanesulfonic acid and, especially, Nafion NR-50
perfluorosulfonic acidic resin which has been cryogenically ground to 60
to 100 mesh (particles having an average diameter of 170 to 250 microns),
available from C. G. Processing of Rockland, Delaware.
The amount of the acidic catalyst which may be used can vary substantially
depending, for example, on process conditions and the particular strong
acid employed. In batch operation of the process, the amount of catalyst
used typically is in the range of 0.5 to 1.5 mole percent based on the
equivalents of initiator.
As is specified hereinabove, the polymerization reaction is carried out in
the presence of tetrahydrofuran which functions as both a comonomer
reactant and as a solvent. If desired, the polymerization reaction may be
preformed in the presence of additional co-solvents, e.g., an inert,
organic solvent such as a hydrocarbon, chlorinated hydrocarbon, and the
like. Specific examples of such solvents include benzene, toluene, xylene,
heptane, methylene chloride, chloroform, and the like. The polymerization
reaction preferably is carried out in the absence of such a co-solvent.
The process of the present invention may be carried out at temperatures in
the range of about 0.degree.-100.degree. C., depending upon the choice of
initiator, catalyst and pressure. Temperatures of about
20.degree.-50.degree. C. are preferred. Reaction pressure is not an
important aspect of the polymerization reaction and, therefore, the
process typically is performed at ambient pressure. However, pressures
moderately above or below atmospheric may be used.
In the operation of our novel process, the primary reactant,
3,4-epoxy-1-butene, is added to a mixture of the acidic catalyst,
tetrahydrofuran, and nucleophilic initiator compound. The
3,4-epoxy-1-butene may be added all at once or very slowly or in stepwise
increments. to a mixture of the catalyst and the initiator. Slow addition
of 3,4-epoxy-1-butene is preferred for controlling the heat of reaction
and product molecular weight. The polymerizations are generally rather
rapid, and reaction is usually complete immediately after complete
addition of 3,4-epoxy-1-butene monomer or up to about 16 hours after
complete addition, depending upon the rate of 3,4-epoxy-1-butene addition,
the amount of tetrahydrofuran used, and catalyst activity.
A preferred embodiment of the polymerization in this invention uses water
or 1,4-butandiol as initiator, 60-100 mesh Nafion.RTM.NR-50 (.RTM.E. I. du
Pont de Nemours & Co.) as catalyst, and an amount of tetrahydrofuran that
is approximately equal to or slightly greater than the amount of
3,4-epoxy-1-butene added at rate of about 1 to 9 equivalents per hour with
rapid stirring and cooling to maintain a reaction temperature below
50.degree. C.
It is apparent from the above process description that the polyether
polymers of the present invention can comprise, in addition to the
3,4-epoxy-1-butene residues, a minor or major amount of the residue of a
nucleophilic initiator compound. For example, if a polymeric initiator,
e.g., a hydroxyl-terminated polyoxyalkylene polymer, is employed and the
number of repeat units of 3,4-epoxy-1-butene residues is relatively low,
the 3,4-epoxy-1-butene residue content of the polymer may be less than 10
weight percent. On the other hand, if the initiator employed is a low
molecular weight compound such as methanol, ethylene glycol, or water, the
3,4-epoxy-1-butene residues may constitute greater than 99 weight percent
of the polymer. The polymers typically comprise at least 80 weight
percent, preferably at least 90 weight percent, 3,4-epoxy-1-butene and
tetrahydrofuran residues. Residues of the initiator compound typically
constitute at least 1 weight percent (at least 0.5 weight percent when
water is the initiator) of the total weight of the polyether polymers.
Our novel polyether polymers preferably are comprised of m units of residue
(1), n units of residue (2), and p units of residue (3) wherein the total
value of m+n+p is about 10 to 40, the value of n/(m+n+p) is in the range
of 0.3 to 0.4, i.e., residue (2) constitutes from 30 to 40 mole percent of
the total moles of residues (1), (2) and (3), the value of n/(m+n) is in
the range of 0.35 to 0.45 and p/(m+n+p) is less than 0.15, i.e., residue
(3) constitutes less than 15 mole percent of the total moles of residues
(1), (2) and (3). The polymers are further characterized in that at least
99% of the terminal groups have the structure:
##STR7##
NMR analyses of the polyethers of the present invention have failed to
detect any secondary, terminal hydroxyl groups. The primary hydroxyl
groups (and thus the polymers) are more reactive for condensation
polymerizations reactions in general. The polyether polymers normally have
a polydispersity value of less than 4, preferably in the range of 1 to 2.
The preferred polyethers contain from about 5 to 20 weight percent, based
on the weight of the polyether polymer, of hydroxyl initiator residues,
preferably residues having the formula --O--R.sup.2 -- derived from a diol
having the formula HO--R.sup.2 --OH wherein R.sup.2 is alkylene of 2 to 6
carbon atoms.
The preparation of the novel polyether polymers of the present invention
and the operation of the process are further illustrated by the following
examples. Proton NMR spectra are obtained on a 300 MHz NMR spectrometers
with samples dissolved in deuterated chloroform containing
tetramethylsilane as an internal standard. The value of n/(m+n+p) is
determined by comparison of the integrated proton NMR absorptions of
residues (1), (2) and (3). Number average molecular weights (Mn) and
polydispersity values (Mw/Mn) are determined using size-exclusion
chromatography with refractive index detection in tetrahydrofuran using
four 10 mm PLgel mixed-bed columns and calibrated using narrow molecular
weight distribution polystyrene standards. Hydroxyl numbers are determined
from titration of the acetic acid formed by the reaction of the sample
with acetic anhydride.
EXAMPLE 1
To a 50-mL reaction flask equipped with nitrogen atmosphere, magnetic
stirbar, and thermocouple are charged 0.10 g (0.091 meq) of Nafion NR-50
resin, (H+ form, 1100 EW, 60-100 mesh), 0.18 g (0.010 moles) water, and
0.94 g (0.013 moles) of tetrahydrofuran. 3,4-Epoxy-1-butene (distilled,
13.6 g, 0.194 moles) is added dropwise with stirring and cooling with an
ice-water bath over a period of about 1.5 hours. The reaction mixture is
filtered to remove the catalyst and the filtrate concentrated using
reduced pressure at 40.degree. C., to give 13 g of a clear, colorless oil
having a value of n/(m+n) of about 0.25, a value of m+n+p of about 18, a
value of n/(m+n+p) of about 0.24, and a value of p/(m+n+p) of about 0.06.
EXAMPLE 2
To a 50-mL reaction flask equipped with nitrogen atmosphere, magnetic
stirbar, and thermocouple are charged 0.10 g (0.091 meq) of Nafion 1100 EW
resin (H+ form, 60-100 mesh), 0.18 g (0.010 moles) water, and 8.71 g
(0.121 moles) of tetrahydrofuran. 3,4-Epoxy-1-butene (distilled, 7.79 g,
0.111 moles) is added dropwise with stirring over a period of about 1.5
hours, giving a reaction temperatures of 35.degree.-40.degree. C. The
reaction mixture is filtered to remove the catalyst. The filtrate is
concentrated using reduced pressure at 40.degree. C., to give 8.06 g of a
clear, colorless oil having a value of n/(m+n) of about 0.42, a value of
m+n+p of about 16, a value of n/(m+n+p) of about 0.33, a value of
p/(m+n+p) of about 0.24, and Mn=1100 and Mw/Mn=2.51.
EXAMPLE 3
To a 50-mL reaction flask equipped with nitrogen atmosphere, magnetic
stirbar, and thermocouple are charged 0.10 g (0.091 meq) of Nafion 1100 EW
(H+ form, 60-100 mesh), 0.18 g (0.010 moles) of water, and 10.0 g (0.139
moles) of tetrahydrofuran. The reaction flask is cooled with an ice-water
bath and 14.0 g (0.200 moles) of 3,4-epoxy-1-butene (distilled) is added
dropwise, with stirring, over a period of about 1.5 hours, giving reaction
temperatures of 5.degree.-10.degree. C. The reaction mixture is filtered
to remove the catalyst and the filtrate is concentrated under reduced
pressure at 40.degree. C., to give 14.6 g of a clear, colorless oil having
a value of n/(m+n) of about 0.42, a value of m+n+p of about 19, a value of
n/(m+n+p) of about 0.37, and a value of p/(m+n+p) of about 0.11.
EXAMPLE 4
To a 250-mL flask equipped with a nitrogen inlet, a reflux condenser, and a
magnetic stirbar was charged 100 mL of tetrahydrofuran, 6.2 g (0.10 mole)
ethylene glycol, and 28 g (0.40 mole) 3,4-epoxy-1-butene. The flask was
cooled with an ice-water bath and the solution was stirred. Then 2 drops
of trifluoromethanesulfonic acid was added, and the solution was stirred
and allowed to warm to room temperature over 24 hours. About 5 drops of
triethyl amine was added to neutralize the catalyst, and the solution was
evaporated under reduced pressure and held under vacuum overnight, giving
38.0 g of a light-yellow syrup having a value of n/(m+n) of about 0.42, a
value of n/(m+n+p) of about 0.38, and a value of p/(m+n+p) of about 0.10.
COMPARATIVE EXAMPLE 1
To a 50-mL reaction flask equipped with nitrogen atmosphere, magnetic
stirbar, and thermocouple are charged 0.10 g (0.091 meq) of Nafion 1100 EW
resin (H+ form, 60-100 mesh), and 0.18 g (0.010 moles) of water.
3,4-Epoxy-1-butene (distilled, 13.6 g, 0.194 moles) is added dropwise to
the catalyst/water mixture over a period of about 1.5 hours while stirring
and cooling with an ice bath. Methylene chloride (10 mL) is added and the
mixture is filtered to remove the catalyst. The filtrate is concentrated
using reduced pressure at 40.degree. C., to give 10 g of a clear,
colorless oil having a value of m+n of about 16 and a value of n/(m+n) of
about 0.20.
COMPARATIVE EXAMPLE 2
To a 50-mL reaction flask equipped with nitrogen atmosphere, magnetic
stirbar, and thermocouple are charged 0.10 g (0.091 meq) of Nafion 1100 EW
resin (H+ form, 60-100 mesh), and 0.18 g (0.010 moles) of
poly(tetramethylene ether) glycol having a number average molecular weight
of 250. 3,4-Epoxy-1-butene (distilled, 13.6 g, 0.194 moles) is added
dropwise over a period of about 1.5 hours while stirring and cooling with
an ice-water bath. Methylene chloride (10 mL) is added and the mixture is
filtered to remove the catalyst. The filtrate is concentrated using
reduced pressure at 40.degree. C., to give 5.8 g of a clear, colorless oil
having a value of m+n of about 18, a value of n/(m+n) of about 0.21, a
value of m+n+p of about 31, a value of n/(m+n+p) of about 0.12, and a
value of p/(m+n+p) of about 0.43, where p repeat units of residue (3) are
derived from the poly(tetramethylene ether) glycol initiator.
EXAMPLE 5
A 1-liter reactor equipped with a stainless steel stirring rod with helical
paddle, a stainless steel cooling coil, and a thermocouple is flushed with
argon and then charged with, in order, water (6.48 g, 0.36 moles), Nafion
1100 EW resin (9.0 g, 9.09 meq, H+ form, 60-100 mesh) and tetrahydrofuran
(30 mL). The reactor is cooled with ice and with chilled water
(5.degree.-10.degree. C.) circulating through the cooling coil.
3,4-Epoxy-1-butene (distilled, 490 g, 6.99 moles) is added by syringe at a
rate of about 100 g per hour giving a reaction temperature of about
11.degree.-18.degree. C. During the addition of the 3,4-epoxy-1-butene,
samples of the reaction mixture are taken periodically and analyzed by
proton NMR for determination of n/(m+n), n/(m+n+p), p/(m+n+p), and m+n+p.
Samples are taken after a total of 140 (Sample 1), 210 (Sample 2), 280
(Sample 3), 350 (Sample 4), 420 (Sample 5) and 490 (Sample 6) g of 3,4
-epoxy-1-butene are added to the reaction mixture. The values of n/(m+n),
n/(m+n+p), p/(m+n+p), and m+n+p are set forth in Table I.
TABLE I
______________________________________
Sam-
ple n/(m + n) n/(m + n + p)
p/(m + n + p)
m + n + p
______________________________________
1 0.27 0.24 0.10 6
2 0.28 0.26 0.08 9
3 0.26 0.24 0.08 11
4 0.27 0.25 0.07 14
5 0.24 0.23 0.07 17
6 0.28 0.27 0.06 19
______________________________________
COMPARATIVE EXAMPLE 3
The procedure of Example 5 is repeated substantially as described except
that no tetrahydro-furan is employed. Values for n/(m+n) and m+n are
determined from samples taken as described in Example 5. These value are
shown in Table II.
TABLE II
______________________________________
Sample n/(m + n) m + n
______________________________________
1 0.12 5
2 0.13 7
3 0.13 9
4 0.15 12
5 0.16 15
6 0.17 17
______________________________________
EXAMPLE 6
The procedure of Example 5 is repeated except that 400 mL of
tetrahydrofuran are used and samples are taken after the addition of a
total of 140, 280, 350, and 490 g of 3,4-epoxy-1-butene. The values of
n/(m+n), n/(m+n+p), p/(m+n+p), and m+n+p are set forth in Table III.
TABLE III
______________________________________
Sam-
ple n/(m + n) n/(m + n + p)
p/(m + n + p)
m + n + p
______________________________________
1 0.38 0.35 0.08 3
2 0.36 0.31 0.08 6
3 0.41 0.38 0.11 8
4 0.42 0.38 0.11 10
______________________________________
As has been mentioned above, the unsaturated polyether polymers provided by
the present invention may be hydrogenated to the corresponding saturated
polymers comprising repeating units of residues having the structure:
##STR8##
The saturated polyethers may be employed in the manufacture of
polyester-ethers useful, for example, in molding compositions. The
following examples illustrate typical hydrogenation procedures which may
be used.
EXAMPLE 7
The unsaturated polyether glycol prepared in Example 1 (10.0 g),
Raney-nickel (1.0 g, prewashed with methanol), and methanol (100 mL) are
charged to a 1-L autoclave equipped with a magnetic stirbar. The
auto-clave is purged with nitrogen, pressurized with 500 psig hydrogen,
then heated to 80.degree. C., with stirring. The reaction mixture is
stirred at 80.degree. C. and 500 psig for 20 hours. After cooling, the
pressure is released, and the reaction mixture is removed, filtered, and
concentrated by evaporating the methanol to give 4.0 g of a clear,
colorless oil comprising m repeat units of residue (4) and p repeat units
of residue (3), wherein the value of m+p is about 18 and the value of
p/(m+p) is about 0.30.
EXAMPLE 8
The unsaturated polyether glycol prepared in Example 2 (5.0 g),
Raney-nickel (0.5 g, prewashed with methanol), and methanol (100 mL) are
charged to a 1-L autoclave equipped with a magnetic stirbar. The autoclave
is purged with nitrogen, pressurized with 500 psig hydrogen, then heated
to 80.degree. C., with stirring. The reaction mixture is stirred at
80.degree. C. and 500 psig for 20 hours. After cooling, the pressure is
released, and the reaction mixture is removed, filtered, and concentrated
by evaporating the methanol to give 4.0 g of a clear, colorless oil
comprising m repeat units of residue (4) and p repeat units of residue
(3), wherein the value of m+p is about 16 and the value of p/(m+p) is
about 0.59.
EXAMPLE 9
The unsaturated polyether glycol prepared in Example 3 (10 g), Raney-nickel
(1.0 g, prewashed with methanol), and methanol (100 mL) are charged to a
1-L autoclave equipped with a magnetic stirbar. The autoclave is purged
with nitrogen, pressurized with 500 psig hydrogen then heated to
80.degree. C. with stirring The reaction mixture is stirred at 80.degree.
C. and 500 psig for 20 hours. After cooling, the pressure is released, and
the reaction mixture is removed, filtered, and concentrated by evaporating
the methanol to give 9.0 g of a clear, colorless oil comprising m repeat
units of residue (4) and p repeat units of residue (3), wherein the value
of m+p is about 19 and the value of p/(m+p) is about 0.48.
The invention has been described in detail with particular reference to
preferred embodiments thereof, but it will be understood that variations
and modifications will be effected within the spirit and scope of the
invention.
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